Activated Internal Alkyne-Based Polymerization^†

As an emerging and efficient polymerization methodology, activated internal alkyne-based polymerization has been considered as a powerful tool for the construction of polymers with diverse architectures and versatile functions. This review focuses on the recent progresses in the polymerization using mono-activated, di-activated, in-situ generated, ring-strained ethynyl groups as substrates, coupling with post-modification on premade polymers containing activated internal ethynyl moieties. Representative examples are used to illustrate the fundamental design strategy, the development of polymerization and post-functionalization, along with the properties and potential applications of the prepared polymers. Moreover, the challenges and perspectives in terms of new-type active alkynes, green polymerization methodology, tailored regio-/stereoselectivity modulation, and potentially expanded application in this area are also discussed.